Diastereoselective cyclopropanation of ketone enols with Fischer carbene complexes

Treatment of aryl/heteroaryl methoxycarbene complexes of chromium with beta-substituted ketone lithium enolates between -78 degrees C and room temperature resulted in the diastereoselective synthesis of 1,2,2,3-tetrasubstituted cyclopropanols. An exception has been observed in the reaction with cyclohexanone lithium enolate that yielded a bicyclic 2-buten-4-olide. 1,2-Dimethoxycyclopropanes and 1-methoxy-2-trimethylsilyloxycyclopropanes were isolated by quenching the reactions with MeOTf or Me3SiCl2 respectively. This novel cyclopropanation process involves formation of lithium (3-oxoalkyl)pentacarbonylchromate intermediates which on warming undergo intramolecular addition to the carbonyl group. This cyclization is equivalent to the cycloplantation in smooth conditions of electron-rich alkenes with Fischer carbene complexes.